Advanced Ligand Field Theory
Fall, Winter, Spring (12 units each)
Instructor: Professor Harry Gray
Course TA: Brian Leigh
Note to Ch 213a prospective students:
This is a tutorial course that involves problem solving in the more advanced levels of ligand field theory. There will be no exams or term papers. Familiarity with elementary quantum mechanics (especially angular momentum, many-electron systems, and approximation methods) and a mastery of group theory at the level of Cotton, Chemical Applications of Group Theory, are required prerequisites. Most students finish this course in a year's time, and you will only be allowed to register for the class when you have completed 75% of the first problem set. Therefore, if you are interested in taking this course, please contact the course instructor prior to formally registering for it.
First Term (Ch213a): Crystal-Field Theory (CFT) is developed in detail for the d3 configuration in fields of high symmetry (including the construction of Tanabe-Sugano diagrams). Then, theory is applied to the analysis of selected absorption and emission spectra of solutions and single crystals. Some discussion of vibrational fine structure in electronic spectra is included. Finally, applications of CFT to the prediction of ligand substitutions (thermal and photochemical) and stereochemistry are presented.
Second Term (Ch213b): Using a
perturbation approach, CFT is extended to include magnetic susceptibilities and
electron paramagnetic resonance (EPR). The Spin Hamiltonian formalism is
treated in detail. Types of magnetic behavior and EPR spectra are illustrated.
Third Term (Ch213c): The student does an individual research project which makes use of concepts presented in the first two terms.
The goal of this course is to present enough of the conceptual and computational aspects of ligand-field theory to the student that the successes and failures of this electronic structure model are clearly delineated. Where appropriate, selected physical techniques are discussed with respect to the types of information they offer concerning the ground and excited states of transition metal ions. Numerous examples will be used to illustrate practical applications of the theory and include coordination and organometallic complexes, minerals, and metal ions in biological systems.